CN110172752A - A kind of mesoporous carbon nano-fiber materials of richness and its preparation method and application - Google Patents

A kind of mesoporous carbon nano-fiber materials of richness and its preparation method and application Download PDF

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CN110172752A
CN110172752A CN201910464141.1A CN201910464141A CN110172752A CN 110172752 A CN110172752 A CN 110172752A CN 201910464141 A CN201910464141 A CN 201910464141A CN 110172752 A CN110172752 A CN 110172752A
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carbon nano
fiber materials
mesoporous carbon
richness
glucose
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CN110172752B (en
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李长明
梁滔滔
张玉环
邹卓
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Southwest University
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Southwest University
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    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • D01F9/14Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
    • D01F9/16Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from products of vegetable origin or derivatives thereof, e.g. from cellulose acetate
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/28Electrolytic cell components
    • G01N27/30Electrodes, e.g. test electrodes; Half-cells
    • G01N27/308Electrodes, e.g. test electrodes; Half-cells at least partially made of carbon
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/28Electrolytic cell components
    • G01N27/30Electrodes, e.g. test electrodes; Half-cells
    • G01N27/327Biochemical electrodes, e.g. electrical or mechanical details for in vitro measurements
    • G01N27/3275Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction
    • G01N27/3278Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction involving nanosized elements, e.g. nanogaps or nanoparticles
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/416Systems
    • G01N27/48Systems using polarography, i.e. measuring changes in current under a slowly-varying voltage

Abstract

The present invention relates to a kind of mesoporous carbon nano-fiber materials of richness and its preparation method and application, belong to field of material technology, this method is first using biomass as raw material, acetic acid bacteria is obtained by soaking fermentation, fermentation hydrogel is made by acetic acid bacteria again, the mesoporous carbon nano-fiber materials of the richness finally are made by carbonization treatment in fermentation hydrogel, the material has significant electric conductivity, with the matched aperture of enzyme size, high specific surface area and good stability, glucose oxidase the material it is mesoporous in being capable of steady load, therefore it can be used for preparing highly sensitive glucose sensor, glucose sensor is prepared with the material, the tedious steps of enzyme load can be effectively reduced, to reduce the preparation cost of enzyme biologic sensor, has higher practical value, and the material preparation method is simple to operation, raw material sources are wide It is general and at low cost, it is suitble to expanded production.

Description

A kind of mesoporous carbon nano-fiber materials of richness and its preparation method and application
Technical field
The invention belongs to field of material technology, and in particular to a kind of mesoporous carbon nano-fiber materials of richness and preparation method thereof and Using.
Background technique
The part that one biosensor is maintained close ties with by two forms: a biological acceptor and an energy converter.Its In middle biological acceptor enzyme be as the most common receptor of discriminance analysis detectable substance, and wherein the fixation of enzyme be design enzyme based sensor Bio-identification in most important part, sensor surface enzyme immobilizatio is essential key in biosensor design Step.
Nano material can be mentioned preferably because its unique performance plays important role in biosensor design The detection performance of high biosensor, has broad prospects, and especially the load of the self assembly to enzyme may be implemented in porous material, Especially mesopore size is distributed in 2-50nm, agrees with compared with the size (4-20nm) of glucose oxidase, will be fixed with to enzyme Fabulous facilitation.
Therefore, the load that a kind of meso-porous carbon material is used for glucose oxidase is studied, is passed for highly sensitive detection glucose Sensor development provides important load substrate, is of great significance to enzyme load factor, sensing stability, detection sensitivity is improved.
Summary of the invention
In view of this, one of the objects of the present invention is to provide a kind of preparation methods of mesoporous carbon nano-fiber materials of richness; The second purpose is to provide a kind of mesoporous carbon nano-fiber materials of richness;The third purpose is to provide a kind of electrochemical sensor;Mesh Four be to provide application of the electrochemical sensor in glucose detection.
In order to achieve the above objectives, the invention provides the following technical scheme:
1, a kind of preparation method of the mesoporous carbon nano-fiber materials of richness, described method includes following steps:
(1) soak is taken after biological material to be impregnated to 240-360h in water at 30 DEG C, obtains bacterium solution;Then by institute It states bacterium solution to be added in acetic acid bacterium culture medium, static culture 120- after 12-48h is cultivated in ventilation in 30 DEG C of incubator after mixing Fermentation hydrogel is made in 240h;
(2) aeroge is obtained after being freeze-dried after fermentation hydrogel obtained in step (1) removal of impurities, then by the gas Gel is pyrolyzed 1-6h in inert atmosphere under the conditions of 500-1100 DEG C, rich mesoporous carbon nano-fiber materials are made.
Preferably, in step (1), the mass volume ratio of the biological material and water is 1-5:10, the quality volume The unit of ratio is g:mL.
Preferably, in step (1), the biological material is fruit and/or pericarp.
Preferably, the fruit is at least one of lemon, passion fruit, pineapple or citrus;The pericarp is lemon, hundred The pericarp of at least one of fragrant fruit, pineapple or citrus fruit.
Preferably, in step (1), the volume ratio of the bacterium solution and acetic acid bacterium culture medium is 2-5:8-10.
2, the mesoporous carbon nano-fiber materials of richness prepared by the method.
3, a kind of electrochemical sensor, including electrochemical workstation, working electrode, to electrode, reference electrode, electrolytic cell and Electrolyte, the working electrode surface are coated with the mesoporous carbon nano-fiber materials of richness, the mesoporous carbon nano-fiber material of richness Glucose oxidase has been loaded on material.
Preferably, the working electrode is prepared as follows:
Glucose oxidase is dispersed in water by 10-50:1 in mass ratio together with rich mesoporous carbon nano-fiber materials, is mixed 24-96h is stood after even at 4 DEG C, takes precipitating after being then centrifuged 2-10min with the revolving speed of 5000-8000r/min, it will be described heavy It forms sediment and is dispersed in water after washing with the matched proportion density of 0.5-2mg/mL, obtain dispersion liquid, binder is added in Xiang Suoshu dispersion liquid, Electrode modification solution is made after mixing, the electrode modification solution is coated on electrode, it is dry;The dispersion liquid and institute The volume ratio for stating binder is 1-5:1.
Preferably, the binder is Nafion solution, and the mass fraction of Nafion is in the Nafion solution 0.1%.
Preferably, the drying is specially the dry 60-120min at 25-50 DEG C.
4, application of a kind of electrochemical sensor in glucose detection.
The beneficial effects of the present invention are: the present invention provides a kind of mesoporous carbon nano-fiber materials of richness and preparation method thereof And application, this method obtains acetic acid bacteria first using biomass as raw material, by soaking fermentation, then fermentation water is made by acetic acid bacteria Finally the mesoporous carbon nano-fiber materials of the richness are made by carbonization treatment in fermentation hydrogel by gel, which has significant Electric conductivity and the matched aperture of enzyme size, high specific surface area and good stability, glucose oxidase is in the material Material it is mesoporous in can steady load, therefore can be used for preparing highly sensitive glucose sensor, grape prepared with the material Sugared sensor, the tedious steps that can effectively reduce enzyme load have higher to reduce the preparation cost of enzyme biologic sensor Practical value, and the material preparation method is simple to operation, and raw material sources are extensive and at low cost, is suitble to expanded production.
Other advantages, target and feature of the invention will be illustrated in the following description to a certain extent, and And to a certain extent, based on will be apparent to those skilled in the art to investigating hereafter, Huo Zheke To be instructed from the practice of the present invention.Target of the invention and other advantages can be realized by following specification and It obtains.
Detailed description of the invention
To make the objectives, technical solutions, and advantages of the present invention clearer, the present invention is made below in conjunction with attached drawing excellent The detailed description of choosing, in which:
Fig. 1 is the field emission scanning electron microscope figure of the mesoporous carbon nano-fiber materials of richness prepared in embodiment 1;(a is in Fig. 1 Field emission scanning electron microscope figure under 30000 times, b is the field emission scanning electron microscope figure under 300000 times in Fig. 1)
Fig. 2 is the transmission electron microscope picture of the richness mesoporous carbon nano-fiber materials and glucose oxidase that prepare in embodiment 1; (a is the transmission electron microscope picture of rich mesoporous carbon nano-fiber materials under 500000 times in Fig. 2, and b is 500000 times of lower glucose in Fig. 2 The transmission electron microscope picture of oxidizing ferment)
Fig. 3 is the X-ray diffractogram of the mesoporous carbon nano-fiber materials of richness prepared in embodiment 1;
Fig. 4 is the impedance diagram of the mesoporous carbon nano-fiber materials of richness prepared in embodiment 1;
Fig. 5 is the graph of pore diameter distribution of the mesoporous carbon nano-fiber materials of richness prepared in embodiment 1;(a is nitrogen suction in Fig. 5 Attached-isothermal curve is desorbed, b is the mesoporous distribution curve of BJH in Fig. 5)
Fig. 6 is the field emission scanning electron microscope figure of the mesoporous carbon nano-fiber materials of richness prepared in embodiment 2;(a is in Fig. 6 Field emission scanning electron microscope figure under 30000 times, b is the field emission scanning electron microscope figure under 300000 times in Fig. 6)
Fig. 7 is the field emission scanning electron microscope figure of the mesoporous carbon nano-fiber materials of richness prepared in embodiment 3;(a is in Fig. 7 Field emission scanning electron microscope figure under 30000 times, b is the field emission scanning electron microscope figure under 300000 times in Fig. 7)
It is -0.8-0V that Fig. 8, which is in potential window width, and sweeping speed is 50mVs-1Under conditions of, the sensing that is constructed in embodiment 1 Cyclic voltammetric response test result figure of the device to glucose;
Fig. 9 is the chrono-amperometric response test knot to glucose that the sensor constructed in embodiment 1 is measured at -0.4V Fruit figure;(timing response curve of a between concentration of glucose and current-responsive in Fig. 9, b is the sensor response time in Fig. 9 Test result figure)
Figure 10 is by the graph of relation between the corresponding concentration of glucose of Fig. 9 and current-responsive;
Figure 11 be in embodiment 1 sensor that constructs to disturbance ingredient selectivity test result figure;(a is in Figure 11 Chronoamperometry is to the testing result figure of chaff interferent, and b is the current-responsive value figure of each chaff interferent and detection in Figure 11)
Figure 12 be in embodiment 1 sensor that constructs to the glucose mark-on reclaims result figure of different serum.
Specific embodiment
Illustrate embodiments of the present invention below by way of specific specific example, those skilled in the art can be by this specification Other advantages and efficacy of the present invention can be easily understood for disclosed content.The present invention can also pass through in addition different specific realities The mode of applying is embodied or practiced, the various details in this specification can also based on different viewpoints and application, without departing from Various modifications or alterations are carried out under spirit of the invention.
Embodiment 1
The rich mesoporous carbon nano-fiber materials of preparation and the working electrode for glucose detection, and construct glucose electrochemistry Sensor (1) presses the mass volume ratio 1:10 of passion fruit Pi Yushui, takes after passion fruit skin is impregnated 240h in water at 30 DEG C Soak obtains bacterium solution;Then the volume ratio 1:4 for pressing bacterium solution and acetic acid bacterium culture medium, bacterium solution is added in acetic acid bacterium culture medium, Fermentation hydrogel is made in static culture 120h after ventilation is cultivated for 24 hours in 30 DEG C of incubator after mixing;Wherein, quality volume The unit g:mL of ratio;
(2) fermentation hydrogel obtained in step (1) is soaked in deionized water after 48h to impurity removal and is freeze-dried After obtain aeroge, then aeroge is placed in tube furnace, is pyrolyzed 4h under the conditions of 900 DEG C in nitrogen atmosphere, is made rich mesoporous Carbon nano-fiber materials.
(3) 25:1 in mass ratio is by the mesoporous carbon nano-fiber materials one of richness obtained in glucose oxidase and step (2) It rises and is dispersed in water, stood for 24 hours at 4 DEG C after mixing, take precipitating after being then centrifuged 5min with the revolving speed of 5000r/min, will sink It forms sediment to be dispersed in water after water washing with the matched proportion density of 1mg/mL, obtains dispersion liquid, mass fraction is added into dispersion liquid is 0.1% Nafion solution is made electrode modification solution, electrode modification solution is coated on screen printing electrode after mixing, Dry 120min, obtains the working electrode for being used for glucose detection at 30 DEG C;Wherein, the volume of dispersion liquid and Nafion solution Than for 1:1;
(4) by the working electrode obtained for glucose detection in step (3) with electrochemical workstation, to electrode (silk Wire mark brush carbon electrode), reference electrode (screen printing carbon electrode), electrolytic cell and electrolyte (concentration 0.01mol/L, pH=7.4 Phosphate buffer solution) be assembled into electrochemical glucose sensor together.
Fig. 1 is the field emission scanning electron microscope figure of the mesoporous carbon nano-fiber materials of richness prepared in embodiment 1, wherein in Fig. 1 A is the field emission scanning electron microscope figure under 30000 times, and b is the field emission scanning electron microscope figure under 300000 times in Fig. 1, can by Fig. 1 Know, which is presented fibrous structure, and form is uniform, and fiber surface is also distributed pore structure abundant.
Fig. 2 is the transmission electron microscope picture of the richness mesoporous carbon nano-fiber materials and glucose oxidase that prepare in embodiment 1, In, a is the transmission electron microscope picture of rich mesoporous carbon nano-fiber materials under 500000 times in Fig. 2, and b is 500000 times of lower grapes in Fig. 2 The transmission electron microscope picture of carbohydrate oxidase, as shown in Figure 2, the aperture of Fu Jiekong carbon nano-fiber materials and the partial size of glucose oxidase Size matching, illustrate glucose oxidase the material it is mesoporous in being capable of steady load.
Fig. 3 is the X-ray diffractogram of the mesoporous carbon nano-fiber materials of richness prepared in embodiment 1, from the figure 3, it may be seen that by 15 ° Wide packet diffraction maximum with 35 ° or so can be seen that the material as carbon nanomaterial, and not detect depositing for other miscellaneous peaks ?.
Fig. 4 is the impedance diagram of the mesoporous carbon nano-fiber materials of richness prepared in embodiment 1, as shown in Figure 4, the electricity of the material Lotus transfer resistance is about 150 ohm.
Fig. 5 is the graph of pore diameter distribution of the mesoporous carbon nano-fiber materials of richness prepared in embodiment 1, wherein a is nitrogen in Fig. 5 Gas adsorption-desorption isothermal curve, b is the mesoporous distribution curve of BJH in Fig. 5, by a in Fig. 5 it is found that the material mesoporous area is up to 550cm2/ g, by b in Fig. 5 it is found that the material mesoporous pore size is distributed in 2-50nm, 80% mesoporous pore size is distributed in 4-50nm.
Embodiment 2
The rich mesoporous carbon nano-fiber materials of preparation and the working electrode for glucose detection, and construct glucose electrochemistry Sensor (1) presses the mass volume ratio 2.5:10 of lemon and water, takes leaching after passion fruit skin is impregnated 360h in water at 30 DEG C Liquid is steeped, bacterium solution is obtained;Then the volume ratio 5:8 for pressing bacterium solution and acetic acid bacterium culture medium, bacterium solution is added in acetic acid bacterium culture medium, is mixed Static culture 180h after 48h is cultivated in ventilation in 30 DEG C of incubator after even, and fermentation hydrogel is made;Wherein, mass volume ratio Unit g:mL;
(2) fermentation hydrogel obtained in step (1) is soaked in deionized water after being removed for 24 hours to impurity and is freeze-dried After obtain aeroge, then aeroge is placed in tube furnace, is pyrolyzed 1h under the conditions of 1100 DEG C in nitrogen atmosphere, is made rich mesoporous Carbon nano-fiber materials.
(3) 10:1 in mass ratio is by the mesoporous carbon nano-fiber materials one of richness obtained in glucose oxidase and step (2) It rises and is dispersed in water, stand 96h after mixing at 4 DEG C, take precipitating after being then centrifuged 10min with the revolving speed of 7000r/min, will sink It forms sediment to be dispersed in water after water washing with the matched proportion density of 0.5mg/mL, obtains dispersion liquid, mass fraction is added into dispersion liquid For 0.1% Nafion solution, electrode modification solution is made after mixing, electrode modification solution is coated to screen printing electrode On, dry 90min, obtains the working electrode for being used for glucose detection at 40 DEG C;Wherein, the body of dispersion liquid and Nafion solution Product is than being 5:1;
(4) by the working electrode obtained for glucose detection in step (3) with electrochemical workstation, to electrode (silk Wire mark brush carbon electrode), reference electrode (screen printing carbon electrode), electrolytic cell and electrolyte (concentration 0.01mol/L, pH=7.4 Phosphate buffer solution) be assembled into electrochemical glucose sensor together.
Fig. 6 is the field emission scanning electron microscope figure of the mesoporous carbon nano-fiber materials of richness prepared in embodiment 2, wherein in Fig. 6 A is the field emission scanning electron microscope figure under 30000 times, and b is the field emission scanning electron microscope figure under 300000 times in Fig. 6, can by Fig. 6 Know, which is presented fibrous structure, and form is uniform, and fiber surface is also distributed pore structure abundant.
Embodiment 3
The rich mesoporous carbon nano-fiber materials of preparation and the working electrode for glucose detection, and construct glucose electrochemistry Sensor (1) presses the mass volume ratio 5:10 of orange peel and water, takes leaching after passion fruit skin is impregnated 300h in water at 30 DEG C Liquid is steeped, bacterium solution is obtained;Then the volume ratio 4:9 for pressing bacterium solution and acetic acid bacterium culture medium, bacterium solution is added in acetic acid bacterium culture medium, is mixed Static culture 240h after 12h is cultivated in ventilation in 30 DEG C of incubator after even, and fermentation hydrogel is made;Wherein, mass volume ratio Unit g:mL;
(2) fermentation hydrogel obtained in step (1) is soaked in deionized water after 96h to impurity removal and is freeze-dried After obtain aeroge, then aeroge is placed in tube furnace, is pyrolyzed 6h under the conditions of 500 DEG C in nitrogen atmosphere, is made rich mesoporous Carbon nano-fiber materials.
(3) 50:1 in mass ratio is by the mesoporous carbon nano-fiber materials one of richness obtained in glucose oxidase and step (2) It rises and is dispersed in water, stand 48h after mixing at 4 DEG C, take precipitating after being then centrifuged 2min with the revolving speed of 8000r/min, will sink It forms sediment to be dispersed in water after water washing with the matched proportion density of 2mg/mL, obtains dispersion liquid, mass fraction is added into dispersion liquid is 0.1% Nafion solution is made electrode modification solution, electrode modification solution is coated on screen printing electrode after mixing, Dry 60min, obtains the working electrode for being used for glucose detection at 50 DEG C;Wherein, the volume of dispersion liquid and Nafion solution Than for 3:1;
(4) by the working electrode obtained for glucose detection in step (3) with electrochemical workstation, to electrode (silk Wire mark brush carbon electrode), reference electrode (screen printing carbon electrode), electrolytic cell and electrolyte (concentration 0.01mol/L, pH=7.4 Phosphate buffer solution) be assembled into electrochemical glucose sensor together.
Fig. 7 is the field emission scanning electron microscope figure of the mesoporous carbon nano-fiber materials of richness prepared in embodiment 3, wherein in Fig. 6 A is the field emission scanning electron microscope figure under 30000 times, and b is the field emission scanning electron microscope figure under 300000 times in Fig. 6, can by Fig. 6 Know, which is presented fibrous structure, and form is uniform, and fiber surface is also distributed pore structure abundant.
Embodiment 4
10 μ L 1M glucose solutions (solvent is PBS buffer solution) are added to the electricity of the sensor constructed in embodiment 1 It solves in liquid, is -0.8-0V in potential window width, sweeping speed is 50mVs-1Under conditions of test the sensor to the circulation of glucose Volt-ampere response, while being responded using cyclic voltammetric of the sensor to PBS buffer solution as blank control.As a result as shown in figure 8, As shown in Figure 8, which has good electrochemical response to glucose.
Embodiment 5
Chronometry, the sensor constructed in testing example 1 are used under the crest voltage (- 0.4V) of cyclic voltammetry curve To the response of the chrono-amperometric of glucose, it is added in the electrolyte for the sensor that when test continuously constructs into embodiment 1 different dense The relationship of the glucose solution (increasing to 8mM from 0.2mM) of degree, time interval 100s, recording responses time and current value is bent Line to get the sensor to the ampere response diagram of glucose, as a result as shown in Figure 9, wherein in Fig. 9 a be concentration of glucose and electricity The timing response curve between response is flowed, b is sensor response time test result figure in Fig. 9, as shown in Figure 9, is added not After the glucose of concentration, sensor current response is continuously increased and reaches steady-state current within the faster time, responds Time is less than 3.4s;Graph of relation between concentration of glucose and current-responsive is obtained by Fig. 9, as shown in Figure 10, by Figure 10 It is found that the current-responsive of the sensor is that good linear relationship, linear equation is presented within the scope of 0.2-8mM in concentration of glucose For Y=-5.95+3.98X, R2=0.998, detection is limited to 40nM, and sensitivity is 56.3 μ AmM-1·cm-2
Embodiment 6
Using chronoamperometry, 10 μ L concentration are separately added into 10mL electrolyte in the sensor that constructs in embodiment 1 Glucose and concentration for 0.05mM are the ascorbic acid (AA), dopamine (DA), uric acid (UA), sodium chloride (Na of 0.5mM+And Cl-) and potassium nitrate (K+And NO3-) response test has been carried out, as a result as shown in figure 11, wherein a is chronoamperometry in Figure 11 To the testing result figure of chaff interferent, b is the current-responsive value figure of each chaff interferent and detection in Figure 11, as shown in Figure 11, with grape Sugar comparison, the sensor is smaller for the electrochemical response of other reducing substances, other surveys of reducing substances to glucose Examination causes minimum interference, which has fabulous selectivity to the detection of glucose.
Embodiment 7
Using the sensor constructed in chronoamperometry and standard samples recovery detection embodiment 1 to the glucose of different serum Electrochemical response, testing result is as shown in figure 12, as shown in Figure 12, observes the amount of serum mark-on reclaims of different batches not Together, for the rate of recovery in 78.8%-109.6%, detection range and human body fasting plasma glucose concentration in conjunction with the sensor are about 2.8- 7.8mM or so illustrates that the detection of glucose in human serum may be implemented in sensor, provides reliably for the development of Novel glucometer Detection method.
Finally, it is stated that the above examples are only used to illustrate the technical scheme of the present invention and are not limiting, although referring to compared with Good embodiment describes the invention in detail, those skilled in the art should understand that, it can be to skill of the invention Art scheme is modified or replaced equivalently, and without departing from the objective and range of the technical program, should all be covered in the present invention Scope of the claims in.

Claims (10)

1. a kind of preparation method of the mesoporous carbon nano-fiber materials of richness, which is characterized in that described method includes following steps:
(1) soak is taken after biological material to be impregnated to 240-360h in water at 30 DEG C, obtains bacterium solution;Then by the bacterium Liquid is added in acetic acid bacterium culture medium, and static culture 120-240h after 12-48h is cultivated in ventilation in 30 DEG C of incubator after mixing, Fermentation hydrogel is made;
(2) aeroge is obtained after being freeze-dried after fermentation hydrogel obtained in step (1) removal of impurities, then by the aeroge 1-6h is pyrolyzed under the conditions of 500-1100 DEG C in inert atmosphere, rich mesoporous carbon nano-fiber materials are made.
2. the method as described in claim 1, which is characterized in that in step (1), the quality volume of the biological material and water Than being g:mL for the unit of 1-5:10, the mass volume ratio.
3. method according to claim 2, which is characterized in that in step (1), the biological material is fruit and/or fruit Skin.
4. the method as described in claim 1, which is characterized in that in step (1), the volume of the bacterium solution and acetic acid bacterium culture medium Than for 2-5:8-10.
5. by the mesoporous carbon nano-fiber materials of richness of the described in any item method preparations of claim 1-4.
6. a kind of electrochemical sensor, including electrochemical workstation, working electrode, to electrode, reference electrode, electrolytic cell and electrolysis Liquid, which is characterized in that the working electrode surface is coated with the mesoporous carbon nano-fiber materials of richness described in claim 5, the richness Glucose oxidase has been loaded on mesoporous carbon nano-fiber materials.
7. a kind of electrochemical sensor as claimed in claim 6, which is characterized in that the working electrode is made as follows It is standby:
Glucose oxidase is dispersed in water by 10-50:1 in mass ratio together with rich mesoporous carbon nano-fiber materials, after mixing 24-96h is stood at 4 DEG C, takes precipitating after being then centrifuged 2-10min with the revolving speed of 5000-8000r/min, and the precipitating is washed It is dispersed in water after washing with the matched proportion density of 0.5-2mg/mL, obtains dispersion liquid, binder is added in Xiang Suoshu dispersion liquid, mix Electrode modification solution is made afterwards, the electrode modification solution is coated on electrode, it is dry;The dispersion liquid is glued with described The volume ratio for tying agent is 1-5:1.
8. a kind of electrochemical sensor as claimed in claim 7, which is characterized in that the binder is Nafion solution, institute The mass fraction for stating Nafion in Nafion solution is 0.1%.
9. a kind of electrochemical sensor as claimed in claim 7, which is characterized in that the drying is specially at 25-50 DEG C Dry 60-120min.
10. a kind of application of the described in any item electrochemical sensors of claim 6-9 in glucose detection.
CN201910464141.1A 2019-05-30 2019-05-30 Mesoporous-carbon-rich nanofiber material and preparation method and application thereof Expired - Fee Related CN110172752B (en)

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CN111326743A (en) * 2019-12-09 2020-06-23 中国人民解放军军事科学院军事医学研究院 Application of porous carbon derived from bamboo as electrode material for glucose biosensing and glucose biofuel cell
CN113552098A (en) * 2020-04-24 2021-10-26 中国人民大学 Pathogenic bacteria biosensing analysis method based on mesoporous membrane size effect

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